Graphene modified “black {0 0 1}TiO2” nanosheets for photocatalytic oxidation of ethylene: The implications of chemical surface characteristics in the reaction mechanism

Abstract

In this work, crystal facets, bandgap, size and shape of reduced graphene oxide (rGO) modified anatase {001} black TiO2 nanosheets (rGO-B-TiO2 NSTs) were tailored for the photocatalytic oxidation of ethylene under high humidity content. XRD, Raman and HR-TEM analyses confirm that rGO-B-TiO2 NSTs have a 94 % of exposed {001} facets with high number of oxygen vacancies. In addition, rGO-B-TiO2 NSTs exhibit increased values of surface area and porosity compared to its pristine form. A 48 and 34 μmol g−1 of ethylene are adsorbed at the surface of rGO-B-TiO2 NSTs in the absence and in the presence of humidity, respectively. In addition, operando DRIFTS analyses provide the insight of surface interactions between ethylene molecules and adsorption sites of rGO-B-TiO2 NSTs. The photocatalytic removal efficiencies of the synthesized materials under both UV and visible light irradiation proceed as follows: rGO-B-TiO2 NSTs > B-TiO2 NSTs > TiO2 NSTs > commercial TiO2 NPs. Further, ethylene is very quickly photocatalytic oxidized when rGO-B-TiO2 NSTs is applied under UV light irradiation, having a 72 and 92 % ethylene removal in the absence and in the presence of humidity, respectively. Moreover, a 48 and 58 % of ethylene removal takes place in the absence and presence of humidity under visible light irradiation, respectively. Results indicate that rGO-B-TiO2 NSTs boost the photocatalytic activity through their virtue of visible-light absorption properties (Bandgap = 2.61 eV) and the rapid electron-hole separation at the rGO {001} black TiO2 NSTs interfaces. Such findings are confirmed through UV-visible diffused reflectance, photoelectrochemical and photoluminescence analyses. Nanosheets made of rGO modified {001} black TiO2 could be used as an effective photocatalyst for the removal of ethylene from large volume fruit storage areas by exploiting a simple light source in the presence of high content of humidity.